Certain 4-halo-5-aryl-1,2,3-dithiazole compounds and their preparation

ABSTRACT

4-HALO-5-ARYL-1,2,3-DITHIAZOLE, USEFUL AS FUNGICIDES, OVICIDES, INSECTICIDES AND HERBICIDES, ARE PREPARED BY REACTING A N-aryl cyanothioformamide and a sulfur dihalide in the presence of a catalytic amount of a formamide compound or quaternary ammonium salt.

BACKGROUND OF THE INVENTION

Patterson et al., "Ring Index", 2nd Ed., page 11, disclose3H-1,2,4-dithiazole, 1,2-dithiazolidine, 1,3,4,-dithiazole and1,3,4,-dithiazolidine.

U.S. Pat. No. 3,419,573, issued to Weinstock on Dec. 31, 1968, disclosesthe preparation of 1,2,5-thiadiazoles by the reaction of sulfur chlorideand a cyanoformimidate.

U.S. Pat. No. 3,763,176, issued to G. K. Kohn and M. S. Singer on Oct.2, 1973, discloses the preparation of 3-halo-5-alkyl-delta²-thiadiazolin-4-one by the reaction of a sulfur dihalide and a N-alkylcyanoformamide.

DESCRIPTION OF THE INVENTION

The dithiazole compounds of the invention may be represented by theformula ##STR1## wherein X is fluoro, chloro, bromo or iodo, and Ar isphenyl, naphthyl, phenyl or naphthyl substituted with 1 to 3 of the sameor different substituents selected from hydroxy, fluoro, chloro, bromo,iodo, cyano, nitro, benzoyl, formyl, alkanoyl of 2 to 6 carbon atoms,alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 2 carbon atoms and 1 to5 of the same or different halogens selected from fluoro, chloro, iodo,or bromo, alkoxy of 1 to 4 carbon atoms, phenoxy, phenoxy substitutedwith 1 to 2 of the same or different substituents selected from hydroxy,fluoro, chloro, bromo, iodo, trifluoromethyl, trichloromethyl, nitro,cyano or alkyl of 1 to 4 carbon atoms.

A preferred class of dithiazole compounds is that wherein X is chloro orbromo and Ar is phenyl, naphthyl, or phenyl substituted with 1 to 2 ofthe same or different substituents selected from fluoro, chloro, bromo,iodo, cyano, nitro, benzoyl, alkyl of 1 to 4 carbon atoms,trifluoromethyl, trichloromethyl, tribromomethyl, phenoxy or phenoxysubstituted with 1 to 2 of the same or different substituents selectedfrom fluoro, chloro, bromo, iodo, nitro, trifluoromethyl,trichloromethyl or alkyl of 1 to 4 carbon atoms.

Another preferred class of dithiazole compounds is that wherein Ar isphenyl, naphthyl, phenyl or naphthyl substituted with 1 to 2 of the sameor different substituents selected from fluoro, chloro, bromo, iodo,trifluoromethyl, trichloromethyl, tribromomethyl, alkyl of 1 to 4 carbonatoms or nitro.

The most preferred class of dithiazole compounds is that wherein X ischloro or bromo and Ar is phenyl, naphthyl or phenyl substituted with 1to 2 of the same or different substituents selected from fluoro, chloro,bromo, iodo or alkyl of 1 to 4 carbon atoms.

Representative dithiazole compounds of the invention include:

4-bromo-5-phenylimino-1,2,3-dithiazole

4-chloro-5-(4-hydroxyphenylimino)-1,2,3-dithiazole

4-fluoro-5-(1-naphthylimino)-1,2,3-dithiazole

4-chloro-5-(2-chloronaphth-1-ylimino)-1,2,3-dithiazole

4-chloro-5-(2-nitronaphth-1-ylimino)-1,2,3-dithiazole

4-bromo-5-(5-cyanonaphth-2-ylimino)-1,2,3-dithiazole

4-chloro-5-(4-iodophenylimino)-1,2,3-dithiazole

4-chloro-5-(4-chloromethylphenylimino)-1,2,3-dithiazole

4-chloro-5-(4-phenoxyphenylimino)-1,2,3-dithiazole

4-bromo-5-(3-trichloromethylphenylimino)-1,2,3-dithiazole

4-bromo-5-(3-formylphenylimino)-1,2,3-dithiazole

4-chloro-5-(4-acetylphenylimino)-1,2,3-dithiazole

4-chloro-5-(4-acetoxyphenylimino)-1,2,3-dithiazole

4-chloro-5-(3-methoxyphenylimino)-1,2,3-dithiazole

4-chloro-5-(4-[4-chlorophenoxy]phenylimino)-1,2,3-dithiazole, and

4-chloro-5-(3-[4-cyanophenoxy]phenylimino)-1,2,3-dithiazole.

The dithiazole compounds of the invention are prepared by reacting asulfur dihalide and a N-aryl cyanothioformamide, as depicted by thefollowing reaction: ##STR2## wherein Ar and X have the same significanceas previously defined.

Reaction (1) is generally conducted by reacting substantially equimolaramounts of the sulfur dihalide and the cyanothioformamide, e.g., themolar ratios of sulfur dihalide (III) to cyanothioformamide (II)generally vary from about 1.5:1 to 1:1.5, although molar ratios fromabout 1.1:1 to 1:1.1 are preferred. Preferably, reaction (1) isconducted in the presence of catalytic amount of a formamide compound ora quaternary ammonium salt. Generally, amounts of formamide compound orquaternary ammonium salt per mol of sulfur dihalide vary from about 0.01to 0.3, although amounts from 0.05 to 0.2 mols per mol of sulfurdihalide are preferred. Suitable formamide compounds includeN,N-dialkylformamides and N-alkylformamides wherein the alkyl group(s)has from 1 to 4 carbon atoms, e.g., N-methylformamide,N,N-dimethylformamide or N,N-diethylformamide. Suitable quaternaryammonium salts are tetralkylammonium halides wherein the alkyl has 1 to6 carbon atoms and the halide is fluoro, chloro, bromo or iodo, e.g.,tetramethylammonium chloride or tetrabutylammonium bromide. When aquaternary salt is employed as a catalyst, the anion is preferable thesame halide as the halide of the sulfur dihalide reactant.

In general, reaction (1) is accomplished by reacting thecyanothioformamide (IV), the sulfur dihalide (III) and the formamide orquaternary salt catalyst in an inert liquid organic diluent. Suitableinert diluents include alkanes and haloalkanes, such as hexane,isooctane, or dichloromethane; aromatic compounds, such as benzene,toluene, chlorobenzene; oxygenated hydrocarbon such as acyclic alkylethers, such as dimethoxyethane and dibutyl ether; and cyclic etherssuch as dioxane, tetrahydrofuran and tetrahydropyran. Generally, theamount of diluent employed ranges from 1 to 50 mols per mol of sulfurdihalide.

The reaction is suitable conducted at a temperature of 0° C to theboiling point of the diluent, although temperatures between 0° C and100° C are preferred. Generally, however, the conversion of thedithiazole hydrochloride salt (V) to the product (I) requires elevatedtemperatures, e.g., about 30° C to 100° C. The reaction is conducted ator above atmosphere pressure. The reaction time will, of course, varydepending on the reaction temperature and the particular reactantsemployed. Generally, however, the reaction time varies from one-halfhour to 24 hours. The progress of the reaction can sometimes bedetermined by the evolution of hydrogen halide gas from the reactionmixture and the completion of the reaction can sometimes be determinedby the cessation of gas evolution.

The chlorodisulfide intermediate (IV) and the dithiazole hydrohalidesalt (V) formed in the reaction (1) are generally not isolated and areconverted directly to the dithiazole (I) during the course of thereaction.

The N-aryl cyanothioformamide reactant (II) is a known compound, and isgenerally prepared by the reaction of an aryl isothiocyanate and a metalcyanide, as disclosed in U.S. Pat. No. 3,287,102, issued Nov. 22, 1966to J. F. Olin.

EXAMPLE 1 Preparation of 4-chloro-5-phenylimino-1,2,3-dithiazole

A solution of 13.5 g (0.1 mol) phenyl isothiocyanate and 6.5 g (0.1 mol)potassium cyanide in 100 ml ethanol and 40 ml water was stirred at about25° C for 1 hour. The solution was then diluted with water, slurriedwith charcoal and filtered. The filtrate was acidified with concentratedhydrochloric acid. An oil was separated on acidification. The oilsolidified on standing and the resulting solid was filtered. The solidwas then recrystallized from benzene/hexane to give 12.8 g N-phenylcyanothioformamide, as a orange solid melting at 73°-81° C.

A solution of 10.0 g N-phenyl cyanothioformamide in 50 mldimethoxyethane was added dropwise over a period of 40 minutes to anice-bath cooled solution of 7 g sulfur dichloride in 200 mldimethoxyethane. Ten drops of dimethylformamide and 0.5 g oftetraethylammonium chloride were added to the resulting solution. Thereaction mixture was then stirred for 24 hours. A solid separated fromthe reaction mixture. The solid was filtered and heated in 25 ml benzeneuntil gas evolution ceased and a homogeneous solution was obtained. Thebenzene was then evaporated to give an oil. The oil was crystallizedfrom hexane to give 10 g of 4-chloro-5-phenylimino-1,2,3-dithiazole, asa bright yellow solid melting at 63°-65° C. The compound and itselemental analysis are tabulated in Table I as compound No. 1.

EXAMPLE 2 Preparation of 4-chloro-5-(2-methyl-4-chlorophenylimino)-1,2,3-dithiazole

A 50 ml sample of water was added slowly to 18 g 2-methyl-4-chlorophenylisothiocyanate and 7 g potassium cyanide in 150 ml ethanol. Theresulting dark red solution was stirred at about 25° C for 18 hours. Thereaction mixture was then diluted with about 800 ml water, decolorizedwith charcoal and acidified with concentrated hydrochloric acid. A solidseparated. The solid was filtered, taken up in benzene, decanted from alittle water, treated with charcoal and diluted with hexane. On cooling,9.8 g of N-(2-methyl-4-chlorophenyl) cyanothioformamide crystallized asan orange solid, m.p. 105°-106° C.

A solution of 4 g sulfur dichloride in 25 ml dichloromethane was addeddropwise over 55 minutes to a solution of 7.5 gN-2-methyl-4-chlorophenyl cyanothioformamide and 1 g tetraethylammoniumchloride in 50 ml dichloromethane. Gas was evolved from the reactionsolution. The reaction solution was stirred at ambient temperature(about 25° C) for 18 hours during which time a solid separated (5.3 g).Recrystallization of the solid from benzene/hexane gave4-chloro-5-(2-methyl-4-chlorophenylimino)-1,2,3-dithiazole as yellowcrystals, m.p. 130°-131° C. The product and its elemental analysis aretabulated in Table I as compound No. 2.

EXAMPLE 3 Preparation of 4-chloro-5-(3-4-dichlorophenylimino)-1,2,3-dithiazole

A 13 g sample of N-(3,4-dichlorophenyl) cyanothioformamide in 50 mldimethoxyethane was added dropwise over 40 minutes to a cooled (icebath) solution of 7.4 g sulfur dichloride in 50 ml dimethoxyethane. Theice bath was removed and 0.5 g of dimethylformamide was added to thereaction mixture. The reaction was then stirred at about 25° C for 3hours, during which time a yellow solid separated. The yellow solid wasfiltered and heated under reflux in 50 ml toluene for 10 minutes duringwhich time gas was evolved and the reaction mixture became homogenous.The toluene was then evaporated under reduced pressure to give a solidresidue. The residue recrystallized from hexane/benzene to give 11. g ofproduct, as a yellow solid, m.p. 89°-90° C. The product and itselemental analysis are tabulated in Table I as compound No. 5.

Other compounds of the invention were prepared by procedures similar tothose of Examples 1-3. These compounds are reported in Table I.

FUNGICIDAL UTILITY

The compounds of the invention are useful for controlling fungi,particularly plant fungal infections caused by Botrytis cinerea, leafblights caused by organisms such as Pythrium ultimum, Helminthosporumsativum, Fusarium moniliforme, Rhizoctonia solani, Monolinia fructicolaand Uromyces phaseoli typica. However, some fungicidal compounds of theinvention may be more fungicidally active than others against particularfungi.

When used as fungicides, the compounds of the invention are applied infungicidally effective amounts to fungi and/or their habitats, such asvegetative hosts and non-vegetative hosts, e.g., animal products. Theamount used will, of course, depend on several factors such as the host,the type of fungus and the particular compound of the invention. As withmost pesticidal compounds, the fungicides of the invention are notusually applied full strength, but are generally incorporated withconventional, biologically inert extenders or carriers normally employedfor facilitating dispersion of active fungicidal compounds, recognizingthat the formulation and mode of application may affect the activity ofthe fungicide. Thus, the fungicides of the invention may be formulatedand applied as granules, as powdery dusts, as wettable powders, asemulsifiable concentrates, as solutions, or as any of several otherknown types of formulations, depending on the desired mode ofapplication.

Wettable powders are in the form of finely divided particles whichdisperse readily in water or other dispersant. These compositionsnormally contain from about 5-80% fungicide, and the rest inertmaterial, which includes dispersing agents, emulsifying agents andwetting agents. The powder may be applied to the soil as a dry dust, orpreferably as a suspension in water. Typical carriers include fuller'searth, kaolin clays, silicas, and other highly absorbent, readilywettable, inorganic diluents. Typical wetting, dispersing or emulsifyingagents include, for example: the aryl and alkylaryl sulfonates and theirsodium salts; alkylamide sulfonates, including fatty methyl taurides;alkaryl polyether alcohols, sulfated higher alcohols, and polyvinylalcohols; polyethylene oxides, sulfonated animal and vegetable oils;sulfonated petroleum oils, fatty acid esters of polyhydric alcohols andthe ethylene oxide addition products of such esters; and the additionproducts of long-chain mercaptans and ethylene oxide. Many other typesof useful surface-active agents are available in commerce. Thesurface-active agent, when used, normally comprises from 1% to 15% byweight of the fungicidal composition.

Dusts are freely flowing admixtures of the active fungicide with finelydivided solids such as talc, natural clays, kieselguhr, pyrophyllite,chalk, diatomaceous earths, calcium phosphates, calcium and magnesiumcarbonates, sulfur, lime, flours, and other organic and inorganic solidswhich act as dispersants and carriers for the toxicant. These finelydivided solids have an average particle size of less than about 50microns. A typical dust formulation useful herein contains 75% silicaand 25% of the toxicant.

Useful liquid concentrates include the emulsifiable concentrates, whichare homogeneous liquid or paste compositions which are readily dispersedin water or other dispersant, and may consist entirely of the fungicidewith a liquid or solid emulsifying agent, or may also contain a liquidcarrier such as xylene, heavy aromatic naphthas, isophorone, and othernonvolatile organic solvents. For application, these concentrates aredispersed in water or other liquid carrier, and are normally applied asa spray to the area to be treated.

Other useful formulations for fungicidal applications include simplesolutions of the active fungicide in a dispersant in which it iscompletely soluble at the desired concentration, such as acetone,alkylated naphthalenes, xylene, or other organic solvents. Granularformulations, wherein the fungicide is carried on relatively coarseparticles, are of particular utility for aerial distribution or forpenetration of cover-crop canopy. Pressurized sprays, typically aerosolswherein the active ingredient is dispersed in finely divided form as aresult of vaporization of a low-boiling dispersant solvent carrier, suchas the Freons, may also be used. All of those techniques for formulatingand applying fungicides are well known in the art.

The percentages by weight of the fungicide may vary according to themanner in which the composition is to be applied and the particular typeof formulation, but in general comprise 0.5 to 95% of the toxicant byweight of the fungicidal composition.

The fungicidal compositions may be formulated and applied with otheractive ingredients, including other fungicides, insecticides,nematocides, bactericides, plant growth regulators, fertilizers, etc.

EXAMPLE 4 Tomato Late Blight

Compounds of the invention were tested for the control of the TomatoLate Blight organism Phytophthora infestans conidia. Five- tosix-week-old tomato (variety Bonny Best) seedlings were used. The tomatoplants were sprayed with a 250-ppm solution of the test compound inacetone, water and a small amount of a non-ionic emulsifier. The sprayedplants were then inoculated one day later with the organism, placed inan environmental chamber and incubated at 66°-68° F and 100% relativehumidity for at least 16 hours. Following the incubation, the plantswere allowed to dry and then were maintained at 60-80% relative humidityfor approximately 7 days. The percent disease control provided by agiven test compound was based on the percent disease reduction relativeto untreated check plants. The compounds giving effective control at thetest concentration are tabulated in Table II.

EXAMPLE 5 Tomato Early Blight

Compounds of the invention were tested for the control of the TomatoEarly Blight organism, Alternaria solani conidia. Tomato (variety BonnyBest) seedlings of 6 to 7 weeks old were used. The tomato plants weresprayed with a 250-ppm solution of the test compound in anacetone-and-water solution containing a small amount of a non-ionicemulsifier. The sprayed plants were inoculated one day later with theorganism, dried and maintained at 60-80% relative humidity for about 12days. Percent disease control was based on the percent diseasedevelopment on untreated check plants. The compounds giving effectivecontrol at the test concentration are tabulated in Table III.

EXAMPLE 6 Celery Late Blight

Compounds of the invention were tested for the control of Celery LateBlight using celery (Utah) plants 11 weeks old. The Celery Late Blightorganism was septoria apii. The Celery plants were sprayed withsolutions of the candidate toxicant mixed with acetone, water and anonionic emulsifier. The plants were then inoculated with the organismand placed in an environmental chamber and incubated at 66°-68° F in100% relative humidity for an extended period of time (approximately 48hours). Following the incubation, the plants were allowed to dry andthen were maintained at a 60-80% relative humidity for approximately 14days. The percent disease control provided by a given candidate toxicantis based on the percent disease reduction relative to untreated checkplants. The compounds giving effective control at the testconcentrations are reported in Table IV.

EXAMPLE 7 Botrytis cinerea control

4-chloro-5-(2-methyl-4-chlorophenylimino)-1,2,3-dithiazole was testedfor Botrytis cinerea control using detached, well-developed primaryleaves of a 4-6 week old horsebean plant. The leaves were dipped into a40-ppm solution of the test compound in acetone and water containing asmall amount of a nonionic emulsifier, then taken out and placed in apetri plate lined with two pieces of filter paper. The leaves wereallowed to dry while the filter paper was kept moist by adding water asrequired. The treated leaves were then inoculated with the spores ofBotrytis cinerea fungus grown on potato dextrose agar. The plate wascovered after inoculation and kept at 23.5° C. The filter-paper liningof the plate was kept saturated with water throughout the test. The rateof disease incidence was determined in 3 to 5 days, when the diseasesymptoms were fully evident on non-treated check leaves. The percentagedisease control provided by the test compound was calculated as thepercentage disease reduction based on the non-treated check leaves. Thetest compound was found to give 92% control.

EXAMPLE 8 Powdery Mildew

The powdery mildew test was made using bean seedlings (var. Bountiful)with well-developed primary leaves. The pathogen was Erysiphe polygoni.The bean seedlings were sprayed with a 250-ppm solution of the testcompound in an acetone-water mixture containing a nonionic emulsifier.The treated plants were inoculated one day after spray application ofthe test compound with the pathogen. The plants were then maintained ina greenhouse at a 60-80% relative humidity and at a temperature of68°-70° F. The rate of infection on the leaves was made after about 10days. The percent disease control provided by a given test compound wasbased on the disease reduction relative to untreated check plants. Thecompounds of the invention giving effective control at the testconcentrations are reported in Table V.

EXAMPLE 9 Mycelia Inhibition

The compounds of the present invention were evaluated for fungicidaleffectiveness by means of a mycelial inhibition test. This test isdesigned to measure the fungitoxic activity of fungicidal chemicals interms of their degree of inhibition of mycleium growth. Each compound tobe tested was dissolved in acetone to 500 ppm concentration. Paperstrips were innoculated with the particular mycelium growth by coveringthe paper with a potato dextrose broth culture of mycelial suspension.The innoculated papers were then placed on potato dextrose agar platesand sprayed by means of a micro sprayer with the fungicidal solution.The treated paper strips were incubated at 25° C and data is taken after24 hours. Fungicidal activities are measured by a zone of inhibitedmycelial growth from the center of the paper strip. The effectiveness ofthe compounds tested for fungicidal activity is reported in Table VI interms of the microgram/cm² for 99% control of the fungus.

HERBICIDAL UTILITY

The compounds of the present invention are also herbicidal inpost-emergent applications. For post-emergent applications, theherbicidal compounds will generally be applied directly to the foliageand other plant parts. Generally, the herbicidal compounds of theinvention are effective against weed grasses as well as broadleavedweeds. Some may be selective with respect to the type of applicationand/or type of weed.

The compounds of the present invention can be used alone as herbicides.However, it is generally desirable to apply the compounds in herbicidalcompositions comprising one or more of the herbicidal compoundsintimately admixed with a biologically inert carrier. The carrier may bea liquid diluent or a solid, e.g., in the form of dust, powder orgranules. In the herbicidal composition, the active herbicidal compoundscan be from about 0.01 to 95% by weight of the entire composition.

Suitable liquid diluent carriers such as benzene, toluene, kerosene,diesel oil, fuel oil, and petroleum naphtha. Suitable solid carriers arenatural clays such as kaolinite, atapulgite, and montmorillonite. Inaddition, talcs, pyrophillite, diatomaceous silica, synthetic finesilicas, calcium aluminosilicate and tricalcium phosphate are suitablecarriers. Organic materials such as walnut-shell flour, cottonseedhulls, wheat flour, wood flour or redwood-bark flour may also be used assolid carriers.

The herbicidal composition will also usually contain a minor amount of asurface-active agent. Such surface agents are those commonly known atwetting agents, dispersing agents and emulsifying agents, and can beanionic, cationic or nonionic in character. The herbicidal compositionsmay also contain other pesticides, adjuvants, stabilizers, conditioners,fillers, and the like.

The amount of herbicidal compound or composition administered will varywith the particular plant part or plant growth medium which is to becontacted, the general location of application -- i.e., sheltered areassuch as greenhouses, as compared to exposed areas such as fields -- aswell as the desired type of control. Generally for both pre- andpost-emergent control, the herbicidal compounds of the invention areapplied at rates of 0.2 to 60 kg/ha, and the preferred rate is in therange 0.5 to 40 kg/ha.

EXAMPLE 10 Herbicidal Tests

Post-emergent herbicidal tests with representative compounds of thisinvention were made using the following method.

An acetone solution of the test compound was prepared by mixing 750 mgof the compound, 220 mg of a nonionic surfactant and 25 ml of acetone.This solution was added to approximately 125 ml of water containing 156mg of surfactant.

This test solution was uniformly sprayed on 2 similar pots of 24-day-oldplants (approximately 15 to 25 plants per pot) at a dose of 33 mcg/cm².After the plants had dried, they were placed in a greenhouse and thenwatered intermittently at their bases, as needed. The plants wereobserved periodically for phytotoxic effects and physiological andmorphological responses to the treatment. After 3 weeks, the herbicidaleffectiveness of the compound was rated based on these observations. A0-to-100 scale was used, 0 representing no phytotoxicity and 100representing complete kill. The results of these tests appear in TableVII.

EXAMPLE 11 Mite Control Tests

Compounds of the invention were tested for the control mites and miteeggs by the following procedure.

Pinto bean leaves were invested with two spotted-mites (Tetramuchusurticae). The mites were then allowed to lay eggs on the leaves. After48 hours, the leaves were dipped into a water/acetone solutioncontaining a small amount of a non-ionic surfactant and 40-ppm of thetest compound. The treated leaves were then maintained at 85° F. One dayafter treatment, the mortality of adult mites was determined, and sevendays after treatment, the egg mortality (non-hatching eggs) wasdetermined.

The results for the compounds found to have mite and mite egg controlactivity are tabulated in Table VIII.

                                      TABLE 1                                     __________________________________________________________________________     ##STR3##                                                                                                  Elemental Analysis                               Compound              Melting                                                                              Sulfur   Chlorine                                No.   Ar          Color                                                                             Point, ° C                                                                    Calc.                                                                              Found                                                                             Calc.                                                                              Found                              __________________________________________________________________________    1     φ       yellow                                                                            63-65  28.0 27.1                                                                              15.5 16.5                               2     4-Cl-φ  yellow                                                                            108-109                                                                              24.4 24.7                                                                              27.0 26.0                               3     3,5-Cl.sub.2 -φ                                                                       yellow                                                                            112-114                                                                              21.6 21.4                                                                              35.7 35.7                               4     2-CH.sub.3 -4-CL-φ                                                                    yellow                                                                            130-134                                                                              23.1 23.0                                                                              25.6 25.4                               5     3,4-Cl.sub.2 -φ                                                                       yellow                                                                            89-90  21.6 20.9                                                                              35.7 35.2                               6     2,4-Cl.sub.2 -φ                                                                       yellow                                                                            91-92  21.6 21.2                                                                              35.7 34.9                               7     2-CH.sub.3 -φ                                                                         orange                                                                            92-93  26.4 29.4                                                                              14.6 14.5                               8     3-NO.sub.2 -φ                                                                         yellow                                                                            123-124                                                                              13.0 12.2                                                                              23.4 19.5                               9     2-CH.sub.3 -4-Br.sub.2 -φ                                                             yellow                                                                            120-122                                                                              19.9 18.6                                                                              6.2  6.7                                10    2,6-(CH.sub.3).sub.2 -φ                                                               yellow                                                                            119-120                                                                              25.0 23.3                                                                              13.8 15.9                               11    2,4,6-(CH.sub.3).sub.3 -φ                                                             yellow                                                                             99-100                                                                              23.7 22.7                                                                              13.1 15.1                               12    3-Br-φ  yellow                                                                            54-55  20.9 19.7                                                                              6.5  7.0                                13    2,4-(CH.sub.3).sub.2 -φ                                                               yellow                                                                            92-93  25.0 24.6                                                                              13.8 13.7                               14    2-Cl-φ  orange                                                                            75-76  24.4 23.1                                                                              27.0 28.1                               15    3-Cl-φ  yellow                                                                            56-57  24.4 23.4                                                                              27.0 26.2                               16    2-naphthyl  orange                                                                             99-100                                                                               23.01                                                                             22.7                                                                              12.7 13.0                               17    3-(2-CF.sub.3 -4-NO.sub.2 -φO)φ                                                   yellow                                                                            108-109                                                                              14.8 14.7                                                                              8.2  8.2                                18    3-(4-NO.sub.2 -                                                                phenoxy)-φ                                                                           yellow                                                                            122-123                                                                              17.5 17.9                                                                              9.7  9.9                                19    4-(4-NO.sub.2 -                                                                phenoxy)-φ                                                                           yellow                                                                            133-134                                                                              17.5 17.0                                                                              9.7  10.4                               20    2-(4-NO.sub.2 -                                                                phenoxy)-φ                                                                           yellow                                                                            108-109                                                                              17.5 18.3                                                                              9.7  10.0                               21    2-CH.sub.3 -3-Cl-φ                                                                    yellow                                                                            116-117                                                                              23.1 24.1                                                                              25.6 23.9                               22    2-F-φ   yellow                                                                            73-74  26.0 28.9                                                                              14.4 13.5                               23    4-CN-φ  yellow                                                                            149-151                                                                              25.3 25.8                                                                              16.0 15.3                               24    4-F-φ   orange                                                                            54-55  26.0 26.5                                                                              14.4 14.5                               25    4-CH.sub.3 -φ                                                                         orange                                                                            66-67  26.4 26.6                                                                              14.6 15.2                               26    3,5-Cl.sub.2 -4-OH-φ                                                                  yellow                                                                            132-134                                                                              20.5 20.7                                                                              33.9 32.9                               27    4-benzoyl-φ                                                                           orange                                                                            134-135                                                                              10.7 12.2                                                                              19.3 19.5                               28    2-CH.sub.3 -5-Cl-φ                                                                    yellow                                                                            111-112                                                                              23.1 23.2                                                                              25.6 24.5                               29    2-CN-φ  orange                                                                            131-133                                                                              25.3 25.8                                                                              14.0 13.4                               30    3-(2-CN-4-CF.sub.3 -φO)φ                                                          orange                                                                            --     15.5 15.7                                                                              8.6  8.6                                __________________________________________________________________________

                  TABLE II                                                        ______________________________________                                        Compound      Tomato Late Blight,                                             No.           % Control                                                       ______________________________________                                         8            44                                                              13            63                                                              15            68                                                              16            73                                                              17            62                                                              19            51                                                              20            80                                                              21            63                                                              23            97                                                              ______________________________________                                    

                  TABLE III                                                       ______________________________________                                        Compound      Tomato Early Blight,                                            No.           % Control                                                       ______________________________________                                         6            56                                                              13            44                                                              18            44                                                              21            44                                                              22            50                                                              23            90                                                              ______________________________________                                    

                  TABLE IV                                                        ______________________________________                                        Compound      Celery Late Blight,                                             No.           % Control                                                       ______________________________________                                        17            56                                                              18            64                                                              19            62                                                              20            62                                                              22            80                                                              23            63                                                              29            44                                                              30            80                                                              ______________________________________                                    

                  TABLE V                                                         ______________________________________                                        Compound       Powdery Mildew                                                 No.            % Control                                                      ______________________________________                                        3              76                                                             4              100                                                            9              99                                                             21             100                                                            28             90                                                             ______________________________________                                    

                  TABLE VI                                                        ______________________________________                                        Mycelia Inhibition, micrograms/cm.sup.2 for 99% control                       Compound                                                                      No.     P        R        A      F      B                                     ______________________________________                                        1       >1.7     >1.7     >1.7   >1.7     0.33                                2       0.39     0.33     0.85   1.5    --                                    3       >1.7     0.98     >1.7   >1.7   --                                    4       >1.7     0.63     >1.7   >1.7   --                                    5       >1.7     >1.7     1.1    >1.7   --                                    7       >1.7     >1.7     0.98   >1.7   >1.7                                  8       >1.7     >1.7     >1.7   >1.7    1.3                                  11      >1.7     0.98     >1.7   >1.7   >1.7                                  12      >1.7     1.4      >1.7   >1.7   >1.7                                  13      >1.7     >1.7     1.1    >1.7   >1.7                                  15      >1.7     0.98     >1.7   >1.7   >1.7                                  18      >1.7     0.45     >1.7   >1.7   >1.7                                  19      >1.7     0.88     >1.7   >1.7   --                                    20      >1.7     1.3      >1.7   >1.7   --                                    21      >1.7     1.1      >1.7   >1.7    1.3                                  22      1.4      0.73     1.4    1.3    --                                    23      >1.7     0.6      >1.7   1.4      0.78                                25      --       0.92     1.5    >1.7     0.76                                26      >1.7     1.3      >1.7   >1.7   >1.7                                  ______________________________________                                         P = Pythium ultimum                                                           R = Rhizoctonia solani                                                        A = Aspergillus niger                                                         F = Fusarium moniloforma                                                      B = Botrytis cinerea                                                     

                  TABLE VII                                                       ______________________________________                                        Herbicidal Effectiveness                                                      Com-                                                                          pound                                                                         No.   O       W       C     M      P      L                                   ______________________________________                                        1     0       10      20    85     70     80                                  2     15      85      20    100    95     95                                  3     35      85      55    100    100    100                                 4     20      30      20    70     85     70                                  5     35      55      30    100    100    100                                 6     30      55      35    100    95     100                                 7     0       0       0     70     70     60                                  8     0       0       0     30     40     35                                  9     0       0       0     30     30     25                                  10    0       0       0     60     30     75                                  12    30      30      30    85     55     100                                 13    0       0       0     35     35     50                                  14    0       40      30    93     100    100                                 15    30      45      10    85     80     98                                  16    0       90      20    85     70     100                                 21    0       15      0     50     20     45                                  22    0       20      0     70     70     85                                  24    40      60      60    70     70     100                                 25    30      55      35    90     45     100                                 28    45      65      20    100    95     100                                 ______________________________________                                         O = Wild Oats (Avena fatua)                                                   W = Watergrass (Echinochloa crusgalli)                                        C = Crabgrass (Digitaria sanguinalis)                                         L = Mustard (Brassica arvensis)                                               M = Pigweed (Amaranthus retroflexus)                                          P = Lambsquarter (Chenopodium album)                                     

                  TABLE VIII                                                      ______________________________________                                        Compound   Mite           Mite Eggs                                           No.        Control, %     Control, %                                          ______________________________________                                        3          90             85                                                  4          94             100                                                 5          99             100                                                 6          100            0                                                   9          70             100                                                 12         --             78                                                  13         0              30                                                  14         70             0                                                   19         0              78                                                  21         90             99                                                  22         0              39                                                  28         85             85                                                  ______________________________________                                    

What is claimed is:
 1. A compound of the formula ##STR4## wherein X isfluoro, chloro, bromo, iodo and Ar is phenyl, naphthyl or phenyl ornaphthyl substituted with 1 to 3 of the same or different substituentsselected from hydroxy, fluoro, chloro, bromo, iodo, cyano, nitro,benzoyl, formyl, alkanoyl of 2 to 6 carbon atoms, alkyl of 1 to 6 carbonatoms, haloalkyl of 1 to 2 carbon atoms and 1 to 5 of the same ordifferent halogens selected from fluoro, chloro or bromo, alkoxy of 1 to4 carbon atoms, phenoxy, or phenoxy substituted with 1 to 2 of the sameof different substituents selected from fluoro, chloro, bromo, iodo,trifluoromethyl, trichloromethyl, nitro, cyano or alkyl of 1 to 4 carbonatoms.
 2. The compound of claim 1 wherein X is chloro or bromo.
 3. Thecompound of claim 1 wherein X is chloro or bromo and Ar is phenyl,naphthyl or phenyl substituted with 1 to 2 of the same or differentsubstituents selected from fluoro, chloro, bromo, iodo, cyano, nitro,benzoyl, alkyl of 1 to 4 carbon atoms, trifluoromethyl, trichloromethyl,phenoxy or phenoxy substituted with 1 to 2 of the same or differentsubstituents selected from fluoro, chloro, bromo, iodo, nitro,trifluoromethyl, trichloromethyl, or alkyl of 1 to 4 carbon atoms. 4.The compound of claim 1 wherein X is chloro and Ar is phenyl, naphthylor phenyl substituted with 1 to 2 of the same or different substituentsselected from fluoro, chloro, bromo, iodo, or alkyl of 1 to 4 carbonatoms.
 5. The compound of claim 1 wherein X is chloro and Ar is2-methyl-4-chlorophenyl.
 6. A process for preparing a compound of theformula ##STR5## wherein Ar and X are as defined in claim 1 whichcomprises reacting substantially equimolar amounts of a sulfur dihalidewherein the halide is chloro or bromo and a N-aryl cyanothioformamide ofthe formula ##STR6## wherein Ar is as defined above, in the liquid phaseat a temperature of 0° to 100° C in the presence of a catalytic amountof an N,N-dialkylformamide or an N-alkylformamide wherein the alkylgroups have 1 to 4 carbon atoms, or a quaternary ammonium salt.
 7. Theprocess of claim 6 wherein the sulfur dihalide is sulfur dichloride. 8.The process of claim 7 wherein the N,N-dialkylformamide isN,N-dimethylformamide.
 9. The process of claim 7 wherein the quaternaryammonium salt is a lower-tetraalkylammonium halide salt.